Development of a general copper-catalyzed vinylic Finkelstein reaction-application to the synthesis of the C1-C9 fragment of laingolide B

An efficient and broadly applicable procedure for the copper-catalyzed vinylic Finkelstein reaction is reported. Using a simple, readily available and cheap catalytic system, a broad range of alkenyl iodides and bromides can be smoothly converted to their lower homologues with high yields and full retention of the double bond geometry. Key features of this vinylic Finkelstein reaction are its broad applicability, enabling the conversion of readily available alkenyl iodides to their less available brominated and chlorinated counterparts, and the mild reaction conditions compatible with a range of highly functionalized substrates. The potential of this vinylic halogen exchange reaction in total synthesis and medicinal chemistry was demonstrated by its successful use for the synthesis of the C1-C9 fragment of laingolide B and for the late-stage modification of drug-like molecules. The extension of this halogen exchange to the acetylenic and allenic Finkelstein reactions is also reported. (C) 2016 Elsevier Ltd. All rights reserved.